U.S. patent application number 13/816559 was filed with the patent office on 2014-02-13 for butyl ionomer latex.
This patent application is currently assigned to LANXESS INC.. The applicant listed for this patent is Dana K. Adkinson, Rayner B. Krista, Rui Resendes. Invention is credited to Dana K. Adkinson, Rayner B. Krista, Rui Resendes.
Application Number | 20140045986 13/816559 |
Document ID | / |
Family ID | 45567970 |
Filed Date | 2014-02-13 |
United States Patent
Application |
20140045986 |
Kind Code |
A1 |
Adkinson; Dana K. ; et
al. |
February 13, 2014 |
BUTYL IONOMER LATEX
Abstract
The invention relates to a latex composition wherein the latex
composition comprises a butyl ionomer or partially halogenated
butyl rubber ionomer. The latex composition is formed by dissolving
the butyl ionomer in a suitable solvent, emulsifying the polymer in
the solvent, adding water and optionally a minor amount of a
suitable surfactant system to the emulsion and concentrating the
emulsion to remove the water. The advantages of butyl ionomer latex
include lower emulsifier levels, increased latex stability,
improved interaction and adhesion to polar substrates and surfaces.
Through the judicious choice of emulsifiers and/or washing to
remove excess emulsifier a film with enhanced non-extractable
polymeric antimicrobial function can be created. These properties
of ionomer latex are useful in coatings, dipped goods and sponge
applications.
Inventors: |
Adkinson; Dana K.; (London,
CA) ; Krista; Rayner B.; (Strathroy, CA) ;
Resendes; Rui; (Kingston, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Adkinson; Dana K.
Krista; Rayner B.
Resendes; Rui |
London
Strathroy
Kingston |
|
CA
CA
CA |
|
|
Assignee: |
LANXESS INC.
Sarnia
ON
|
Family ID: |
45567970 |
Appl. No.: |
13/816559 |
Filed: |
August 11, 2011 |
PCT Filed: |
August 11, 2011 |
PCT NO: |
PCT/CA2011/050486 |
371 Date: |
August 21, 2013 |
Current U.S.
Class: |
524/464 ;
524/503; 524/572 |
Current CPC
Class: |
C08L 9/10 20130101; C08J
3/05 20130101; C08L 23/36 20130101; C08K 3/20 20130101 |
Class at
Publication: |
524/464 ;
524/572; 524/503 |
International
Class: |
C08L 9/10 20060101
C08L009/10; C08J 3/05 20060101 C08J003/05; C08K 3/20 20060101
C08K003/20 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 13, 2010 |
US |
61373379 |
Claims
1. A butyl rubber latex composition comprising a butyl rubber
ionomer made from a halogenated butyl rubber reacted with a
nitrogen or phosphorous based nucleophile emulsified in water.
2. The composition according to claim 1, wherein the composition
further comprises a surfactant concentration in the range of from 1
to 30 wt %.
3. The composition according to claim 2, wherein the ionomeric
content of the ionomer is greater than 0.1 mol %.
4. The composition according to claim 2, wherein the emulsion is
stable at room temperature.
5. The composition according to claim 2, wherein the emulsion has a
solids content in the range of from 7 to 80 wt %.
6. A butyl rubber latex composition comprising a butyl rubber
ionomer made from a halogenated butyl rubber reacted with a
nitrogen or phosphorous based nucleophile having an ionomeric
content of greater than 0.1 mol % emulsified in water to form a
stable emulsion at room temperature having a solids content in the
range of from 7 to 80 wt %.
7. The composition according to claim 6, wherein the surfactant
concentration of the ionomer is in the range of from 1 to 30 wt
%.
8. A process for making a butyl rubber latex composition
comprising: a. preparing a first solution of a butyl rubber ionomer
comprising a nitrogen or phosphorous based nucleophile in a polar
organic solvent and adding a fatty acid to the solution; b.
preparing a second solution of water having a basic pH and a
surfactant; and, c. mixing the first and second solutions to form a
latex emulsion.
9. The process according to claim 8, wherein the ionomer has an
ionomeric content of greater than 0.1 mol %
10. The process according to claim 8, wherein the emulsion is
stable at room temperature
11. The process according to claim 8, wherein the emulsion has a
solids content of from 7 to 80 wt %.
12. The process according to claim 8, wherein the second solution
comprises a basic amine.
13. The process according to claim 12, wherein the basic amine
comprises an aminoalcohol.
14. The process according to claim 8, wherein the surfactant in the
second solution is present in a concentration of from 1 to 30 wt
%.
15. The process according to claim 8, wherein the polar solvent is
halogenated.
16. The process according to claim 15, wherein the polar solvent
comprises chloromethane, dichloromethane or chloroform.
17. The composition according to claim 2, wherein the composition
further comprises a high aspect ratio filler.
18. The composition according to claim 6, wherein the composition
further comprises a high aspect ratio filler.
19. The process according to claim 8, wherein the process further
comprises mixing a high aspect ratio filler with the butyl ionomer
prior to preparing the first solution.
Description
FIELD OF THE INVENTION
[0001] The invention relates to the process of preparing a
synthetic latex starting from a butyl ionomer or partially
halogenated butyl rubber ionomers.
BACKGROUND
[0002] Poly(isobutylene-co-isoprene), or IIR, is a synthetic
elastomer commonly known as butyl rubber which has been prepared
since the 1940's through the random cationic copolymerization of
isobutylene with small amounts of isoprene. As a result of its
molecular structure, IIR possesses superior air impermeability, a
high loss modulus, oxidative stability and extended fatigue
resistance.
[0003] Butyl rubber is understood to be a copolymer of an isoolefin
and one or more, preferably conjugated, multiolefins as
co-monomers. Commercial butyl comprises a major portion of
isoolefin and a minor amount, not more than 2.5 mol %, of a
conjugated multiolefin. Butyl rubber or butyl polymer is generally
prepared in a slurry process using methyl chloride as a diluent and
a Friedel-Crafts catalyst as part of the polymerization initiator.
This process is further described in U.S. Pat. No. 2,356,128 and
Ullmann's Encyclopedia of Industrial Chemistry, volume A 23, 1993,
pages 288-295.
[0004] Halogenation of this butyl rubber produces reactive allylic
halide functionality within the elastomer. Conventional butyl
rubber halogenation processes are described in, for example,
Ullmann's Encyclopedia of Industrial Chemistry (Fifth, Completely
Revised Edition, Volume A231 Editors Elvers, et al.) and/or "Rubber
Technology" (Third Edition) by Maurice Morton, Chapter 10 (Van
Nostrand Reinhold Company .COPYRGT. 1987), particularly pp.
297-300.
[0005] CA 2,418,884 and 2,458,741 describe the preparation of
butyl-based, peroxide-curable compounds which have high multiolefin
content. Specifically, CA 2,418,884 describes the continuous
preparation of IIR with isoprene levels >4.1 mol %. Halogenation
of this high multiolefin butyl rubber produces a reactive allylic
halide functionality within the elastomer. With these elevated
levels of isoprene now available, it is possible to generate BIIR
analogues which contain allylic bromide functionalities ranging
from greater than 3 mol %.
[0006] The presence of allylic halide functionalities allows for
nucleophilic alkylation reactions. It has been recently shown that
treatment of brominated butyl rubber (BIIR) with nitrogen and/or
phosphorus based nucleophiles, in the solid state, leads to the
generation of IIR-based ionomers with interesting physical and
chemical properties (see: Parent, J. S.; Liskova, A.; Whitney, R.
A; Resendes, R. Journal of Polymer Science, Part A: Polymer
Chemistry 43, 5671-5679, 2005; Parent, J. S.; Liskova, A.;
Resendes, R. Polymer 45, 8091-8096, 2004; Parent, J. S.; Penciu,
A.; Guillen-Castellanos, S. A.; Liskova, A.; Whitney, R. A.
Macromolecules 37, 7477-7483, 2004). The ionomer functionality is
generated from the reaction of a nitrogen or phosphorous based
nucleophile and the allylic halide sites in the BIIR to produce an
ammonium or phosphonium ionic group respectively. The physical
properties of these BIIR based ionomers (green strength, modulus,
filler interactions etc.) are superior to those of their
non-ionomeric counterpart.
[0007] It has been previously discovered that the addition of
para-methylstyrene to the mixed feed of butyl polymerizations
(MeCl, IB and IP mixed feed, with AlCl.sub.3/H.sub.2O as initiator)
results in a high molecular weight polymer with up to 10 mol % of
styrenic groups randomly incorporated along the polymer chain
(Kaszas, U.S. Pat. No. 6,960,632; Kaszas et al. Rubber Chemistry
and Technology, 2001, 75, 155). The incorporation of
para-methylstyrene is found to be uniform throughout the molecular
weight distribution due to the similarity in reactivity with
isobutylene. The isoprene moieties within the butyl terpolymers can
be halogenated by conventional methods.
[0008] A copolymer may be formed comprising a C.sub.4-C.sub.7
isomonoolefin, such as isobutylene, and a comonomer, such as
para-alkylstyrene, preferably para-methylstrene, wherein some of
the alkyl substituent groups present in the styrene monomer units
contain a benzylic halogen or other functionality copolymer.
Additional functional groups can be incorporated by nucleophilic
displacement of the benzylic halogen with a variety of nucleophiles
as described in U.S. Pat. No. 5,162,445. Use of tertiary amines and
phosphines results in the formation of ionomers with improved
physical properties from these copolymers.
[0009] The preparation and use of butyl latex has been reported
previously (see for example U.S. Pat. Nos. 2,944,038, 3,005,804,
3,983,062, 7,119,138, WO 2006/115729, WO 2005/063871, WO
2005/061608). However, one of the biggest factors in the
preparation of these latexes is the ease of making the latex and
the final stability of the latex. The stability of the latex is
commonly achieved by the use of surfactants. While surfactants act
as stabilizers during production, they typically have a detrimental
effect on the properties of a dry latex film, for example, due to
their tendency to migrate and adversely affect the end use
properties of the material (i.e. adhesion, resistance to the growth
of microbes). Surfactants may also cause the unwanted blooming that
leads to surface irregularities in the resulting latex that is
applied to a substrate. Once a latex film is formed surfactants
will leach or be extracted when in contact with aqueous solutions.
It would therefore be desirable to reduce or eliminate the need for
surfactants in forming a butyl latex.
[0010] U.S. Pat. No. 7,238,736 describes the improved filler
dispersion observed when using butyl ionomers as compared to
regular butyl resulting in articles with improved tensile strength.
It would be desirable to provide improved filler dispersion in a
butyl latex.
[0011] U.S. Pat. No. 7,915,333 describes compositions where
improved barrier properties are observed with butyl ionomers and
nanocomposites while maintaining tensile properties. It would be
desirable to provide improved barrier properties in a butyl
latex.
[0012] WO2010/091499 describes butyl ionomer compositions having
anti-microbial and anti-bacterial properties. It would be desirable
to provide improved anti-microbial properties in a butyl latex.
[0013] U.S. Pat. No. 7,662,480 describes improved adhesion of butyl
ionomers to a substrate as compared to a non-ionomeric butyl
rubber. It would be desirable to provide improved coating adhesion
in a butyl latex.
[0014] There is therefore a need for improved butyl latexes,
preferably exhibiting some or all of the above desirable
properties.
SUMMARY OF THE INVENTION
[0015] According to an aspect of the present invention, there is
provided a butyl rubber latex composition comprising a butyl rubber
ionomer. The butyl rubber ionomer may be made from a halogenated
butyl rubber, which may be reacted with a nitrogen or phosphorous
based nucleophile. The ionomeric content of the ionomer may be
greater than 0.1 mol %. The ionomer may be emulsified in water and
may for a stable emulsion at room temperature. The solids content
of the composition may be in the range of from 7 to 80 wt %. The
latex is desirably free of surfactants and/or surfactant residues
or has reduced surfactant and/or surfactant residue content. The
surfactant concentration may be in the range of from 1 to 15 wt %,
1 to 20 wt %, or 1 to 30 wt %. The composition may be useful in the
formation of un-cured articles, such as dipped articles, blown
films or calendered films, or surface coatings for articles, such
as paints.
[0016] According to another aspect of the invention, there is
provided a process for making a butyl rubber latex composition
comprising: preparing a first solution of a butyl rubber ionomer
comprising a nitrogen or phosphorous based nucleophile in a polar
organic solvent and adding a fatty acid to the solution; preparing
a second solution of water having a basic pH and a surfactant; and,
mixing the first and second solutions to form a latex emulsion.
[0017] According to yet another aspect of the present invention,
there is provided a surface coating for an article, the coating
comprising a butyl rubber latex comprising a butyl rubber
ionomer.
[0018] The resulting butyl rubber latex (and coatings made
therefrom) advantageously has improved stability with reduced
occurrence of blooming as compared with conventional non-ionomeric
butyl rubber latexes. The resulting butyl rubber latex (and
coatings made therefrom) also desirably exhibits superior physical
properties, superior barrier properties, superior anti-microbial
properties and superior adhesion as compared with conventional
non-ionomeric butyl rubber latexes. The process for creating the
butyl rubber latex is easier to control and operate than
conventional butyl rubber latex processes, due to the
simplification arising from reducing or eliminating the need for
surfactants.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention provides for a butyl rubber latex
comprising, generally, a butyl rubber ionomer or a partially
halogenated butyl rubber ionomer. The terms butyl rubber ionomer or
partially halogenated butyl rubber ionomer are referred to
collectively herein as "ionomer."
[0020] The ionomer of the present invention is prepared from a
halogenated butyl rubber polymer. Butyl rubber polymers are
generally derived from at least one isoolefin monomer, at least one
multiolefin monomer and optionally further copolymerizable
monomers.
[0021] In one embodiment, the ionomer may comprise repeating units
derived from an isoolefin monomer and a conjugated diene monomer.
In another embodiment, the butyl ionomer may comprise repeating
units derived from an isoolefin monomer and a styrenic monomer. In
yet another embodiment, the butyl ionomer may comprise repeating
units derived from an isoolefin monomer, a conjugated diene monomer
and a styrenic monomer. In embodiments comprising repeating units
derived from a conjugated diene monomer, the number of olefin bonds
derived from such units may comprise a conventional amount or an
elevated amount of greater than 2.2 mol %, greater than 3.0 mol %,
greater than 4.1 mol %, greater than 5.0 mol %, greater than 6.0
mol %, greater than 7.0 mol %, greater than 7.5 mol %, or greater
than 8.0 mol %.
[0022] The butyl rubber polymer is not limited to a specific
isoolefin. Any isoolefin, as known to those of skill in the art,
are contemplated by the present invention including isoolefins
having, for example, within the range of from 4 to 16 carbon atoms.
In one embodiment of the present invention, isoolefins having from
4-7 carbon atoms are contemplated. Examples of isoolefins for use
in the present invention include isobutene, 2-methyl-1-butene,
3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene and
mixtures. A preferred isoolefin is isobutene (isobutylene).
[0023] Similarly, the butyl rubber polymer is not limited to a
specific multiolefin. Multiolefins copolymerizable with the
isoolefins, as known to one skilled in the art, can be used in the
practice of the present invention. Suitable multiolefins include,
for example, those having in the range of from 4-14 carbon atoms.
Examples of suitable multiolefins include isoprene, butadiene,
2-methylbutadiene, 2,4-dimethylbutadiene, piperyline,
3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentylbutadiene,
2-methly-1,5-hexadiene, 2,5-dimethly-2,4-hexadiene,
2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopenta-diene,
methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene and
mixtures thereof. Multiolefin monomers comprising a conjugated
diene are preferred. A particularly preferred conjugated diene is
isoprene.
[0024] In another embodiment of the present invention, the butyl
rubber may further include an additional co-monomer, as known to
those of skill in the art, other than the above referenced
multiolefins. Co-monomers include monomers copolymerizable with the
isoolefins and/or dienes. Co-monomers suitable for use in the
present invention include, for example, styrenic monomers, such as
alkyl-substituted vinyl aromatic co-monomers, including but not
limited to a C.sub.1-C.sub.4 alkyl substituted styrene. Specific
examples of such co-monomers include, for example, .alpha.-methyl
styrene, p-methyl styrene, chlorostyrene, cyclopentadiene and
methylcyclopentadiene. In this embodiment of the present invention,
the butyl rubber polymer may include, for example, random
copolymers of isobutylene, isoprene and para-methylstryene.
[0025] In yet another embodiment of the present invention, an
isoolefin monomer, as described above, is polymerized with a
styrenic monomer, for example an alkyl-substituted vinyl aromatic
co-monomer, including but not limited to a C.sub.1-C.sub.4 alkyl
substituted styrene. Specific examples of styrenic monomers
include, for example, .alpha.-methyl styrene, p-methyl styrene,
chlorostyrene, cyclopentadiene and methylcyclopentadiene. In this
embodiment, the butyl rubber polymer may include, for example,
random copolymers of isobutylene and para-methylstryene.
[0026] Butyl rubber polymers, as described above, are formed from a
mixture of monomers described herein. In one embodiment, the
monomer mixture comprises from about 80% to about 99% by weight of
an isoolefin monomer and from about 1% to 20% by weight of a
multiolefin monomer. In another embodiment, the monomer mixture
comprises from about 85% to about 99% by weight of an isoolefin
monomer and from about 1% to 15% by weight of a multiolefin
monomer. In certain embodiments of the present invention three
monomers may be employed. In these embodiments, the monomer mixture
comprises about 80% to about 99% by weight of isoolefin monomer,
from about 0.5% to about 5% by weight of a multiolefin monomer and
from about 0.5% to about 15% by weight a third monomer
copolymerizable with the isoolefin or multiolefin monomer. In one
embodiment, the monomer mixture comprises from about 85% to about
99% by weight of an isoolefin monomer, from about 0.5% to about 5%
by weight of a multiolefin monomer and from about 0.5% to about 10%
by weight of a third monomer copolymerizable with the isoolefin or
multiolefin monomers. In yet another embodiment, the monomer
mixture comprises from about 80% to about 99% by weight of an
isoolefin monomer and from about 1% to 20% by weight of a styrenic
monomer.
[0027] Once the butyl rubber polymer is formed from the monomer
mixture, the butyl rubber polymer may be subjected to a
halogenation process in order to form the halogenated butyl rubber
polymer or halobutyl rubber polymer. Bromination or chlorination
can be performed according to the process known by those skilled in
the art as in, for example, the procedures described in Rubber
Technology, 3rd Ed., Edited by Maurice Morton, Kluwer Academic
Publishers, pp. 297-300 and further documents cited therein.
[0028] In one embodiment of the present invention, the ionomers may
be prepared from a halogenated butyl rubber polymer having from 0.5
to 2.2 mol % of the multiolefin monomer. For example, a halogenated
butyl rubber for use in the present invention includes a
halogenated butyl rubber having isobutylene and less than 2.2 mole
percent isoprene which is commercially available from LANXESS
Deutschland GmbH and sold under the name BB2030. In another
embodiment of the present invention, the ionomers may be prepared
from a halogenated butyl rubber polymer having a higher multiolefin
content, for example greater than 2.5 mol %. In yet another
embodiment, the ionomers may be prepared from a halogenated butyl
rubber having a multiolefin content of greater than 3.5 mol %. In
still another embodiment, the multiolefin content of the
halogenated butyl rubber is greater than 4.0 mol %. In even another
embodiment, the multiolefin content of the halogenated butyl rubber
is greater than 7.0 mol %. The preparation of a suitable high
multiolefin butyl rubber polymer, for use in the present invention,
is described in co-pending application CA 2,418,884, which is
incorporated herein by reference.
[0029] During halogenation of the butyl polymer, some or all of the
multiolefin content of the butyl polymer is converted to allylic
halides. These allylic halide sites in the halobutyl polymer result
in repeating units derived from the multiolefin monomers originally
present in the butyl polymer. The total allylic halide content of
the halobutyl polymer may not exceed the starting multiolefin
content of the parent butyl polymer. The allylic halide sites allow
for reacting with and attaching a nucleophile to the halobutyl
polymer. In one embodiment of the present invention, the allylic
halide sites of the halobutyl polymer are reacted with at least one
nitrogen or phosphorus containing nucleophile having the following
formula,
##STR00001##
wherein, A is a nitrogen or phosphorus; and, R.sub.1, R.sub.2 and
R.sub.3 are selected from the group consisting of linear or
branched C.sub.1-C.sub.18 alkyl substituents, an aryl substituent
which is monocyclic or composed of fused C.sub.4-C.sub.8 rings,
and/or a hetero atom selected from, for example, B, N, O, Si, P,
and S.
[0030] Nucleophiles for use in the present invention include, for
examples, those nucleophiles having at least one neutral nitrogen
or phosphorus center which possesses a lone pair of electrons that
are electronically and sterically accessible for participation in
nucleophilic substitution reactions. Suitable nucleophiles, for use
in the present invention include, for examples, trimethylamine,
triethylamine, triisopropylamine, tri-n-butylamine,
trimethylphosphine, triethylphosphine, triisopropylphosphine,
tri-n-butylphosphine, triphenylphosphine, diphenylphosphinostyrene,
allyldiphenylphosphine, diallylphenylphosphine,
diphenylvinylphosphine, triallylphosphine, 2-dimethylaminoethanol,
1-dimethylamino-2-propanol, 2-(isopropylamino)ethanol,
3-dimethylamino-1-propanol, N-methyldiethanolamine,
2-(diethylamino)ethanol, 2-dimethylamino-2-methyl-1-propanol,
2-[2-(dimethylamino)ethoxy]ethanol, 4-(dimethylamino)-1-butanol,
N-ethyldiethanolamine, triethanolamine, 3-diethylamino-1-propanol,
3-(diethylamino)-1,2-propanediol,
2-{[2-(dimethylamino)ethyl]methylamino}ethanol,
4-diethylamino-2-butyn-1-ol, 2-(diisopropylamino)ethanol,
N-butyldiethanolamine, N-tert-butyldiethanolamine,
2-(methylphenylamino)ethanol, 3-(dimethylamino)benzyl alcohol,
2-[4-(dimethylamino)phenyl]ethanol, 2-(N-ethylanilino)ethanol,
N-benzyl-N-methylethanolamine, N-phenyldiethanolamine,
2-(dibutylamino)ethanol, 2-(N-ethyl-N-m-toluidino)ethanol,
2,2'-(4-methylphenylimino)diethanol,
tris[2-(2-methoxyethoxy)ethyl]amine, 3-(dibenzylamino)-1-propanol,
N-vinyl caprolactam, N-vinyl phthalimide, 9-vinyl carbazole, or
N-[3-(Dimethylamino)propyl]methacrylamide, and mixtures
thereof.
[0031] In one embodiment of the present invention, the amount of
nucleophile reacted with the butyl rubber may be in the range of
from 0.05 to 5 molar equivalents. In another embodiment, the amount
of nucleophile reacted with the butyl rubber may be in the range of
from 0.5 to 4 molar equivalents. In yet another embodiment, the
ratio of nucleophile reacted with the butyl rubber is 1 to 3 molar
equivalents. The ratios of nucleophile to butyl rubber are based on
the total molar amount of allylic halide present in the halobutyl
polymer.
[0032] As stated above, the nucleophile reacts with the allylic
halide functionality of the halobutyl polymer resulting in units of
ionomeric moieties where the allylic halide functionality existed
on the halobutyl polymer. The total content of ionomeric moiety in
the butyl ionomer may not exceed the starting amount of allylic
halide in the halobutyl polymer; however, residual allylic halides
and/or residual multiolefins may be present. In embodiments of the
present invention where substantially all of the allylic halides
sites are reacted with the nucleophile, a butyl rubber ionomer is
formed. In embodiments where less than all the allylic halide sites
are reacted with the nucleophile, a partially halogenated butyl
rubber ionomer is formed.
[0033] In one embodiment of the present invention, the resulting
ionomer possesses an ionic content of at least 0.1 mol % of the
ionomeric moiety up to an amount not exceeding the original allylic
halide content of the halobutyl polymer used to produce the butyl
ionomer. In another embodiment, the ionomer possesses an ionic
content of at least 0.5 mol % of the ionomeric moiety up to an
amount not exceeding the original allylic halide content of the
halobutyl polymer used to produce the butyl ionomer. In yet another
embodiment, the ionomer possesses an ionic content of at least 1.0
mol % of the ionomeric moiety up to an amount not exceeding the
original allylic halide content of the halobutyl polymer used to
produce the butyl ionomer. In yet another embodiment, the ionomer
possesses an ionic content of at least 1.5 mol % of the ionomeric
moiety up to an amount not exceeding the original allylic halide
content of the halobutyl polymer used to produce the butyl
ionomer.
[0034] In some cases, residual allylic halides may be present in an
amount of from 0.1 mol % up to an amount not exceeding the original
allylic halide content of the halobutyl polymer used to produce the
butyl ionomer. In other embodiments, residual multiolefin may be
present in an amount of from 0.1 mol % up to an amount not
exceeding the original multiolefin content of the butyl polymer
used to produce the halobutyl polymer. In one embodiment, the
residual multiolefin content of the ionomer is at least 0.2 mol %.
In another embodiment, the residual multiolefin content of the
ionomer is at least 0.6 mol %. In yet another embodiment, the
residual multiolefin content of the ionomer is least 0.8 mol %. In
yet another embodiment, the residual multiolefin content of the
ionomer is least 1.0 mol %. In yet another embodiment, the residual
multiolefin content of the ionomer is at least 2.0 mol %. In yet
another embodiment, the residual multiolefin content of the ionomer
is least 3.0 mol %. In yet another embodiment, the residual
multiolefin content of the ionomer is at least 4.0 mol %.
[0035] In one embodiment of the present invention, the ionomer may
comprise repeating units derived from at least one isoolefin
monomer, at least 0.2% of repeating units derived from at least one
multiolefin monomer, and at least one nitrogen or phosphorous based
nucleophile. The butyl rubber ionomer or partially halogenated
butyl rubber ionomer may be formed by preparing a monomer mixture
comprising the isoolefin and a multiolefin, reacting the monomer
mixture to form a polymer, halogenating the polymer to form halo
functional sites on the polymer, and reacting the halo functional
sites with the nucleophile.
[0036] Although it is desirable to reduce or eliminate the need for
surfactants, the butyl rubber latex according to the invention may
include minor amounts of surfactants for use as emulsifiers in
improving emulsification of the rubber/solvent mixture in water.
These surfactants can be, but are not limited to, anionic,
cationic, nonionic or ampoteric surfactants. Surfactants which may
be used are those which are known from and conventionally used in
the field of polymer dispersion. The surfactants are generally
added to the aqueous phase. The following may be used, for example,
as surfactants in the process according to the invention: aliphatic
and/or aromatic hydrocarbons with 8 to 30 carbon atoms which have a
hydrophilic terminal group such as a sulphonate, sulphate,
carboxylate, phosphate or ammonium terminal group. Furthermore,
non-ionic surfactants with functional groups, such as polyalcohols,
polyethers and/or polyesters are suitable as emulsifiers. In
principle, any conventional industrial surfactants which are
suitable for stabilizing polymer dispersions in water may be used.
The following are preferably used as surfactants: fatty acids salts
such as the sodium and/or potassium salts of oleic acid, the
corresponding salts of alkylaryl sulphonic acids, naphthyl
sulphonic acid and their condensation products with, for instance,
formaldehyde, and the corresponding salts of alkylsuccinic acids
and alkylsulphosuccinic acids. Obviously, it is also possible to
use the emulsifiers in any mixture with each other. Suitable
surfactants include fatty acids, rosin acids and detergent
emulsifiers. The fatty acid may contain 4-28 carbon atoms,
preferably 4-24 carbon atoms, and more preferably 12-24 carbon
atoms. Examples of a suitable fatty acid include oleic acid,
palmitolinic acid, palmitic acid, linoleic acid, linolenic acid,
lauric acid, myristic acid, stearic acid, arachidic acid,
lignoceric acid, arachidonic acid, trans-hexadecenoic acid, elaidic
acid, lactobacillic acid, tuberculostearic acid and cerebronic acid
or mixtures thereof. Surfactant systems may also be based on a
phosphate surfactant, a sulfonate surfactant, surfactants derived
from a carboxylic acid and a base or an anionic surfactant or any
combination thereof. Addition of a polyoxyethylated alkyl phenols
act to suppress foam formation when soaps are used as the
emulsifiers and as a stabilizer of the finished latex. An example
of a suitable polyoxyethylate alkyl phenol includes Triton X.TM..
An example of a polyvinyl alcohol based surfactant is Elvanol.TM..
The surfactant concentration may be from 1 to 15 wt %, from 1 to 20
wt %, from 1 to 26 wt %, from 1 to 29 wt %, or from 1 to 30 wt %
calculated on a dry weight basis of the final composition.
[0037] Suitable solvents to form the latex include hexane, heptane,
octane, isooctane, nonane, decane, dichloromethane, toluene,
cyclohexane, pentane, carbon tetrachloride, trichloroethylene, and
methyl ethyl ketone. Addition of a base along with the fatty acid
produces a soap in situ, which functions as the main emulsifier.
Suitable bases include but are not limited to sodium hydroxide,
lithium hydroxide, ethanolamine, potassium hydroxide or mixtures
thereof.
[0038] After emulsification, the solvent is removed from the
emulsion. Additionally, the solution can be heated above
100.degree. C. to remove water if a concentrated latex is desired.
A preferred solids content is from 5 to 90 wt %, from 6 to 80 wt %,
from 6 to 30 wt %, from 30 to 70 wt %, or from 40 to 60 wt %.
[0039] The butyl rubber ionomer latex composition according to the
present invention may include one or more fillers. Suitable fillers
for use in the present invention are composed of particles of a
mineral, such as, for example, silica, silicates, clay, bentonite,
vermiculite, nontronite, beidelite, volkonskoite, hectorite,
saponite, laponite, sauconite, magadiite, kenyaite, ledikite,
gypsum, alumina, titanium dioxide, talc and the like, as well as
mixtures thereof.
[0040] Further examples of suitable fillers include: [0041] highly
dispersable silicas, prepared e.g. by the precipitation of silicate
solutions or the flame hydrolysis of silicon halides, with specific
surface areas of 5 to 1000, preferably 20 to 400 m.sup.2/g (BET
specific surface area), and with primary particle sizes of 10 to
400 nm; the silicas can optionally also be present as mixed oxides
with other metal oxides such as Al, Mg, Ca, Ba, Zn, Zr and Ti;
[0042] synthetic silicates, such as aluminum silicate and alkaline
earth metal silicate; [0043] magnesium silicate or calcium
silicate, with BET specific surface areas of 20 to 400 m.sup.2/g
and primary particle diameters of 10 to 400 nm; [0044] natural
silicates, such as kaolin and other naturally occurring silica;
[0045] natural clays, such as montmorillonite and other naturally
occurring clays; [0046] organophilically modified clays such as
organophilically modified montmorillonite clays (e.g. Cloisite.RTM.
Nanoclays available from Southern Clay Products) and other
organophilically modified naturally occurring clays; [0047] glass
fibers and glass fiber products (matting, extrudates) or glass
microspheres; [0048] metal oxides, such as zinc oxide, calcium
oxide, magnesium oxide and aluminum oxide; [0049] metal carbonates,
such as magnesium carbonate, calcium carbonate and zinc carbonate;
[0050] metal hydroxides, e.g. aluminum hydroxide and magnesium
hydroxide or combinations thereof.
[0051] In one embodiment of the present invention, the mineral
filler is silica. In another embodiment the mineral filler is
silica prepared by the carbon dioxide precipitation of sodium
silicate.
[0052] Dried amorphous silica particles suitable for use as mineral
fillers in accordance with the present invention may have a mean
agglomerate particle size in the range of from 1 to 100 microns. In
one embodiment of the present invention, the dried amorphous silica
particles have a mean agglomerate particle size in the range of
from 10 and 50 microns. In another embodiment of the present
invention, the dried amorphous silica particles have a mean
agglomerate particle size in the range of from between 10 and 25
microns. In one embodiment of the present invention, it is
contemplated that less than 10 percent by volume of the agglomerate
particles are below 5 microns or over 50 microns in size. Suitable
amorphous dried silica has, for example, a BET surface area,
measured in accordance with DIN (Deutsche Industrie Norm) 66131, of
between 50 and 450 square meters per gram and a DBP absorption, as
measured in accordance with DIN 53601, of between 150 and 400 grams
per 100 grams of silica, and a drying loss, as measured according
to DIN ISO 787/11, of from 0 to 10 percent by weight. Suitable
silica fillers are commercially sold under the names HiSil 210,
HiSil 233 and HiSil 243 available from PPG Industries Inc. Also
suitable are Vulkasil S and Vulkasil N, commercially available from
Bayer AG.
[0053] Mineral fillers, as used in the present invention, can also
be used alone or in combination with known non-mineral fillers,
such as: [0054] carbon blacks; suitable carbon blacks are
preferably prepared by the lamp black, furnace black or gas black
process and have BET specific surface areas of 20 to 200 m.sup.2/g,
for example, SAF, ISAF, HAF, FEF or GPF carbon blacks; or [0055]
rubber gels, preferably those based on polybutadiene,
butadiene/styrene copolymers, butadiene/acrylonitrile copolymers
and polychloroprene.
[0056] High aspect ratio fillers useful in the present invention
include clays, talcs, micas, etc. with an aspect ratio of at least
1:3. The fillers may include acircular or nonisometric materials
with a platy or needle-like structure. The aspect ratio is defined
as the ratio of mean diameter of a circle of the same area as the
face of the plate to the mean thickness of the plate. The aspect
ratio for needle and fiber shaped fillers is the ratio of length to
diameter. In one embodiment of the present invention, high aspect
ratio fillers have an aspect ratio of at least 1:5. In another
embodiment of the present invention, high aspect ratio fillers have
an aspect ratio at least 1:7. Yet in another embodiment, high
aspect ratio fillers have an aspect ratio 1:7 to 1:200. Fillers in
accordance with the present invention may have, for example, a mean
particle size in the range of from 0.001 to 100 microns In anther
embodiment, fillers have a mean particle size in the range of from
0.005 and 50 microns. In another embodiment, fillers have a mean
particle size in the range of from 0.01 and 10 microns. A suitable
filler may have a BET surface area, measured in accordance with DIN
(Deutsche Industrie Norm) 66131, of between 5 and 200 square meters
per gram.
[0057] In one embodiment of the present invention, high aspect
ratio fillers comprises a nanoclay, such as, for example, an
organically modified nanoclay. The present invention is not limited
to a specific nanoclay; however, natural powdered smectite clays,
such as sodium or calcium montmorillonite, or synthetic clays such
as hydrotalcite and laponite are suitable examples as starting
materials. In one embodiment, the high aspect fillers include
organically modified montmorillonite nanoclays. The clays may be
modified by substitution of the transition metal for an onium ion,
as is known in the art, to provide surfactant functionality to the
clay that aids in the dispersion of the clay within the generally
hydrophobic polymer environment. In one embodiment of the present
invention, onium ions are phosphorus based (eg: phosphonium ions)
and nitrogen based (eg: ammonium ions) and contain functional
groups having from 2 to 20 carbon atoms (eg: NR.sub.4.sup.+ -
MMT).
[0058] The clays may be provided, for example, in nanometer scale
particle sizes, such as, less than 25 .mu.m by volume. In one
embodiment, the particle size is in the range of from 1 to 50
.mu.m. In another embodiment, the particle size is in the range of
from 1 to 30 .mu.m. In yet another embodiment, the particle size is
in the range of from 2 to 20 .mu.m.
[0059] In addition to silica, the nanoclays may also contain some
fraction of alumina. In one embodiment, the nanoclays may contain
from 0.1 to 10 wt % alumina. In another embodiment the nanoclays
may contain from 0.5 to 5 wt % alumina. In yet anther embodiment,
the nanoclays may contain from 1 to 3 wt % alumina.
[0060] Examples of commercially available organically modified
nanoclays suitable for use in the present invention as high aspect
ratio fillers include, for example, those sold under the tradename
Cloisite.RTM. clays 10A, 20A, 6A, 15A, 30B, or 25A. In one
embodiment, the high aspect ratio fillers may be added to the
pre-formed butyl rubber iononmer to form a nanocomposite in an
amount of from 3 to 80 phr. In another embodiment, the amount of
high aspect ratio fillers in the nanocomposite is from 5 to 30 phr.
In yet another embodiment, the amount of high aspect ratio fillers
in the nanocomposite is from 5 to 15 phr.
[0061] In one aspect of the invention, the butyl rubber ionomer
latex exhibits improved adhesion to non-polar substrates, such as
steel, glass or polytetrafluoroethylene, as compared with
non-ionomeric butyl latexes. The improvement in adhesion may be
determined using a planar separation technique, for example using a
Tel-Tac.TM. adhesion test apparatus. The improvement in adhesion
may be from 1 to 25%.
[0062] The butyl rubber ionomer latex may be cured or uncured. When
cured, the butyl rubber ionomer latex may comprise components
derived from a curing system. The choice of curing system suitable
for use is not particularly restricted and is within the purview of
a person skilled in the art. In certain embodiments of the present
invention, curing system may be sulphur-based, peroxide-based resin
based or UV-based. A typical sulfur-based curing system comprises:
(i) a metal oxide, (ii) elemental sulfur and (iii) at least one
sulfur-based accelerator. The use of metal oxides as a component in
the curing system is well known in the art. A suitable metal oxide
is zinc oxide, which may be used in the amount of from about 1 to
about 10. In another embodiment of the present invention, the zinc
oxide may be used in an amount of from about 2 to about 5, parts by
weight per hundred parts by weight butyl polymer in the
nanocomposite. Elemental sulfur, comprising component (ii) of the
preferred curing system is typically used in amounts of from about
0.2 to about 2 parts by weight, per hundred parts by weight butyl
polymer in the composition. Suitable sulfur-based accelerators
(component (iii) of the preferred curing system) may be used in
amounts of from about 0.5 to about 3 parts by weight, per hundred
parts by weight butyl polymer in the composition. Non-limiting
examples of useful sulfur-based accelerators may be selected from
the thiuram sulfides such as tetramethyl thiuram disulfide (TMTD),
the thiocarbamates such as zinc dimethyl dithiocarbamate (ZDC) and
the thiazyl and benzothiazyl compounds such as mercaptobenzothiazyl
disulfide (MBTS). In one embodiment of the present invention, the
sulphur based accelerator is mercaptobenzothiazyl disulfide.
[0063] Peroxide based curing systems may also be suitable for use
in the present invention for butyl rubber ionomer latexes including
residual multiolefin content in excess of about 0.2 mol %. For
example, a peroxide-based curing system may comprises a peroxide
curing agent, for example, dicumyl peroxide, di-tert-butyl
peroxide, benzoyl peroxide, 2,2'-bis(tert.-butylperoxy
diisopropylbenzene (Vulcup.RTM. 40KE), benzoyl peroxide,
2,5-dimethyl-2,5-di(tert-butylperoxy)-hexyne-3,2,5-dimethyl-2,5-
-di(benzoylperoxy)hexane, (2,5-bis(tert.-butylperoxy)-2,5-dimethyl
hexane and the like. One such peroxide curing agent comprises
dicumyl peroxide and is commercially available under the name DiCup
40C. In one embodiment, the peroxide curing agent is used in an
amount of 0.2 to 7 parts per hundred parts of rubber (phr). In
another embodiment, the peroxide curing agent is used in an amount
of 1 to 6 phr. In yet another embodiment, the peroxide curing agent
is used in an amount of about 4 phr. Peroxide curing co-agents can
also be used in the present invention. Suitable peroxide curing
co-agents include, for example, triallyl isocyanurate (TAIC),
commercially available under the name DIAK 7 from DuPont Or
N,N'-m-phenylene dimaleimide know as HVA-2 (DuPont Dow), triallyl
cyanurate (TAC) or liquid polybutadiene known as Ricon D 153
(supplied by Ricon Resins). Peroxide curing co-agents may be used
in amounts equivalent to those of the peroxide curing agent, or
less. The state of peroxide cured articles is enhanced with butyl
polymers containing increased levels of unsaturation, for example a
multiolefin content of at least 0.5 mol %. Additionally, the degree
of unsaturation can be increased by selection of a phosphorous or
nitrogen-based nucleophile containing a pendant vinyl group such as
but not limited to diphenylphosphinestyrene,
allyldiphenylphosphine, diallylphenylphosphine,
diphenylvinylphosphine, triallylphosphine, N-vinyl caprolactam,
N-vinyl phthalimide, 9-vinyl carbazole, or
N-[3-(dimethylamino)propyl]methacrylamide.
[0064] In some embodiments of the present invention, stabilizers,
anti-oxidants, tackifiers, and/or other additives as known to those
of skill in the art may also be added in the usual way and in the
normal amounts.
[0065] In embodiments where the latex composition includes the
ionomer, fillers, curing agents, and/or other additives, the
ingredients used to form the ionomer may be mixed together prior to
dissolving the ionomer in the solvent. The ingredients may be mixed
using conventional compounding techniques. Suitable compounding
techniques include, for example, mixing the ingredients of the
composite together using, for example, an internal mixer, such as a
Banbury mixer, a miniature internal mixer, such as a Haake or
Brabender mixer, or a two roll mill. An extruder also provides good
mixing, and permits shorter mixing times. It is possible to carry
out the mixing in two or more stages, and the mixing can be done in
different apparatus, for example one stage in an internal mixer and
one stage in an extruder. For further information on compounding
techniques, see Encyclopedia of Polymer Science and Engineering,
Vol. 4, p. 66 et seq. (Compounding). Other techniques, as known to
those of skill in the art, are further suitable for compounding.
Additionally, fillers, curing agents, and/or other additives may be
added to the ionomer latex.
[0066] In one embodiment of the present invention, the ionomer
latex may be formed into a shaped article or applied to an existing
article. The article may be made entirely from the ionomer latex.
Alternatively, a portion of the article may comprise the ionomer
latex. The ionomer latex may be provided on the surface of the
article only. The ionomer latex may be attached to the surface, for
example adhesively or via fasteners. The ionomer may be provided as
part of a composite material comprising a plastic. The plastic may
comprise polyethylene, polypropylene, an EP polymer, an EPDM
polymer, or a nylon polymer. The composite material may comprise a
thermoplastic vulcanizate comprising the butyl ionomer and the
plastic material.
[0067] The ionomer latex may be provided as a surface coating for
the article. The surface coating may be in the form of an applied
membrane (of any suitable thickness), a chemical vapour deposit, or
a powder coating. The coating may further comprise a plastic.
[0068] The ionomer latex may be provided, as part of a coating or
otherwise, with the proviso that no additionally added
antibacterial, antifungal or antialgal agents are present,
particularly such agents that could leach out of the coating. The
coating may consist essentially of the ionomer latex, which is
meant to include any fillers or curative agents that may be present
as part of the ionomer latex.
[0069] The article may comprise: a fluid conduit, such as a hose or
pipe; a container, such as a bottle, tote, storage tank, etc.; a
container closure or lid; a seal or sealant, such as a gasket or
caulking; a material handling apparatus, such as an auger or
conveyor belt; a marine vessel or structure, such as a ship, dock,
or oil drilling platform; a cooling tower; a metal working
apparatus, or any apparatus in contact with metal working fluids;
an engine component, such as fuel lines, fuel filters, fuel storage
tanks, gaskets, seals, etc.; a membrane, for fluid filtration or
tank sealing; or, footwear, particularly portions of footwear that
come into direct contact with the foot.
[0070] Additional examples where the butyl rubber ionomer latex may
be used in articles or coatings include, but are not limited to,
the following: appliances, baby products, bathroom fixtures,
bathroom safety, flooring, food storage, garden, kitchen fixtures,
kitchen products, office products, pet products, sealants and
grouts, spas, water filtration and storage, equipment, food
preparation surfaces and equipments, shopping carts, surface
applications, storage containers, footwear, protective wear,
sporting gear, carts, dental equipment, door knobs, clothing,
telephones, toys, catheterized fluids in hospitals, surfaces of
vessels and pipes, coatings, food processing, biomedical devices,
filters, additives, computers, ship hulls, shower walls, tubing to
minimize the problems of biofouling, pacemakers, implants, wound
dressing, medical textiles, ice machines, water coolers, fruit
juice dispensers, soft drink machines, piping, storage vessels,
metering systems, valves, fittings, attachments, filter housings,
linings, and barrier coatings.
[0071] In one aspect of the invention, the ionomer latex exhibits
antibacterial, antifungal and/or antialgal properties. This feature
of the ionomer is believed to be a result of the ionic nature of
the formed ionomer. Although the inventors do not intend to be
bound by theory, it is believe that the ionic nature of the ionomer
imparts antibacterial, antifungal and/or antialgal properties not
observed in typical halogenated butyl rubber.
[0072] The butyl rubber ionomer latex may reduce a population of
and/or prevent accumulation of organisms associated with
bio-fouling, for example bacteria, fungi, algae, mollusca or
arthropoda. In particular, the ionomer latex may be useful in
preventing the growth of a bio-film on at least a surface of an
article comprising the ionomer. Preventing the growth of a bio-film
may comprise preventing the formation of a continuous layer of
organisms associated with bio-fouling over greater than 25%, 50% or
75% of the surface of the article. The ionomer latex may prevent
accumulation of organisms by preventing an increase in population
of the organisms. The ionomer latex may prevent accumulation of
organisms by impeding attachment of the organisms to the article,
particularly the portion or portions of the article comprising the
ionomer. The ionomer latex may reduce the population of the
organisms by killing individual organisms (for example, via cell
membrane disruption) or by inhibiting reproduction of the organisms
(for example, by affecting cellular DNA). A combination of the
aforementioned mechanisms may be present simultaneously.
[0073] The unique properties of butyl ionomers enhance the
performance of butyl ionomer latex. The resulting latex may be
useful in applications which are paint-like wherein a thin layer is
applied and the ionomer latex provides benefits of adhesion,
flexibility, and antimicrobial properties. Additionally, the
resulting latex may be applied in the form commonly used in dipped
goods to provide a coating with improved flexibility in a variety
of applications including chemical protective gloves, face masks,
protective suits. Other uses include low permeability coatings for
sports balls, rubber hoses, inflatable boats and other inflatable
products, bladders used in production and to protect storage tanks,
window sealings, inner tubes for bicycles, as well as tires.
Additionally, the butyl ionomer latex may be used to prepare a
surface for an additional process such as rubber to cord adhesion
in tire manufacturing. Finally, the latex may be spray dried to
form a butyl ionomer powder that may be used in powder coating
applications or the powder may be an additive to a powder
composition. The ionic moieties of butyl based Ionomers exhibit
affinity for each other resulting in a high level polymer chain to
polymer chain interaction which is the basis of their high green
strength and thermoplastic like behavior.
[0074] The ionomer latex according to the present invention may be
used in cured or uncured form.
[0075] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to
those skilled in the art the numerous variations of the details of
the present invention may be made without departing from the
invention as defined in the appended claims.
[0076] The following examples will be used to illustrate particular
embodiments of the invention.
Example 1
[0077] 62.5 g of BB2030.TM. was dissolved in 585 mL of
CH.sub.2Cl.sub.2 followed by the addition of 12.5 g of oleic acid.
Separately, a base solution composed of 5 g of ethanolamine, 3.9 g
of Triton X-100.TM. and 3.4 g of Elvanol.TM. in 125 mL of distilled
and deionized water was prepared. The rubber cement was added to a
high speed blender, and the base solution was slowly added. Upon
completetion of saponification (.about.5 minutes after addition of
base solution), 250 mL of distilled water was added to the blender.
The mixture was continued to blend with an air purge over the top
of the blender opening. After 5 h of mixing, the latex was
separated. Upon separation, the emulsion broke.
Example 2
[0078] 356 g of LANXESS BB2030.TM. and 16.7 g (1.2 molar
equivalents based on allylic bromide content) of triphenylphosphine
(TPP) were premixed on a 6''.times.12'' mill at room temperature
for 3 minutes. The mixture was then passed through a twin screw
extruder at 160.degree. C. Analysis of the final product by .sup.1H
NMR confirmed the complete conversion of all the allylic bromide of
BB2030.TM. to the corresponding ionomeric species with an ionic
content of 0.8 mol %.
Example 3
[0079] 62.5 g of Example 2 was dissolved in 585 mL of
CH.sub.2Cl.sub.2 followed by the addition of 12.5 g of oleic acid.
Separately, a base solution composed of 5 g of ethanolamine, 3.9 g
of Triton X-100.TM. and 3.4 g of Elvanol.TM. in 125 mL of distilled
and deionized water was prepared. The rubber cement was added to a
high speed blender, and the base solution was slowly added. Upon
completion of saponification (.about.5 minutes after addition of
base solution), 250 mL of distilled water was added to the blender.
The surfactant concentration on a dry weight basis was 28.4%. The
mixture was continued to blend with an air purge over the top of
the blender opening. After 5 h of mixing, the solids content of the
resulting latex was determined to be 7.61%. The ionomer latex was
found to be stable.
Example 4
[0080] LANXESS BB2030.TM. was passed through a twin screw extruder
at 160.degree. C. where N,N-dimethylaminoethanol (DMAE) was added
at a rate of 0.4 mL/min. Analysis of the final product by .sup.1H
NMR confirmed the presence of 0.8 mol % ammonium ionic groups.
Example 5
[0081] 62.5 g of Example 4 was dissolved in 585 mL of
CH.sub.2Cl.sub.2 followed by the addition of 12.5 g of oleic acid.
Separately, a base solution composed of 5 g of ethanolamine, 3.9 g
of Triton X-100.TM. and 3.4 g of Elvanol.TM. in 125 mL of distilled
and deionized water was prepared. The rubber cement was added to a
high speed blender, and the base solution was slowly added. Upon
completion of saponification (.about.5 minutes after addition of
base solution), 250 mL of distilled water was added to the blender.
The mixture was continued to blend with an air purge over the top
of the blender opening. After 5 h of mixing, the latex was
separated and the solids content was determined to be 6.23%.
Example 6
[0082] US 2007/0218296 A1, which is incorporated herein by
reference, describes the preparation of high isoprene BIIR. 62.5 g
of high isoprene BIIR was dissolved in 585 mL of CH.sub.2Cl.sub.2
followed by the addition of 12.5 g of oleic acid. Separately, a
base solution composed of 5 g of ethanolamine, 3.9 g of Triton
X-100.TM. and 3.4 g of Elvanol.TM. in 125 mL of distilled and
deionized water was prepared. The rubber cement was added to a high
speed blender, and the base solution was slowly added. Upon
completion of saponification (.about.5 minutes after addition of
base solution), 250 mL of distilled water was added to the blender.
The mixture was continued to blend with an air purge over the top
of the blender opening. After 5 h of mixing, the latex was
separated. Upon separation, the emulsion broke.
Example 7
[0083] 204 g of brominated high isoprene BIIR and 8.04 g (1.2 molar
equivalents based on allylic bromide content of the brominated high
isoprene BIIR) of triphenylphosphine (TPP) were premixed on a
6''.times.12'' mill at room temperature for 3 minutes. The mixture
was then passed through a twin screw extruder at 160.degree. C.
Analysis of the final product by .sup.1H NMR confirmed the complete
conversion of the allylic bromide to the corresponding ionomeric
species with an ionic content of 0.8 mol %.
Example 8
[0084] 62.5 g of Example 7 was dissolved in 585 mL of
CH.sub.2Cl.sub.2 followed by the addition of 12.5 g of oleic acid.
Separately, a base solution composed of 5 g of ethanolamine, 3.9 g
of Triton X-100.TM. and 3.4 g of Elvanol.TM. in 125 mL of distilled
and deionized water was prepared. The rubber cement was added to a
high speed blender, and the base solution was slowly added. Upon
completion of saponification (.about.5 minutes after addition of
base solution), 250 mL of distilled water was added to the blender.
The mixture was continued to blend with an air purge over the top
of the blender opening. After 5 h of mixing, the latex was
separated and the solids content was determined to be 8.06%.
Example 9
[0085] 62.5 g of Example 2 was dissolved in 585 mL of
CH.sub.2Cl.sub.2 followed by the addition of 12.5 g of oleic acid.
Separately, a base solution composed of 3.75 g of ethanolamine, 3 g
of Triton X-100.TM. and 2.6 g of Elvanol.TM. in 95 mL of distilled
water was prepared. The rubber cement was added to a high speed
blender, and the base solution was slowly added. Upon completion of
saponification (.about.5 minutes after addition of base solution),
250 mL of distilled water was added to the blender. The surfactant
concentration on a dry weight basis was 25.9%. The mixture was
continued to blend with an air purge over the top of the blender
opening. After 1.5 h of mixing, the latex was separated and the
solids content was determined to be 9.4%. The ionomer latex was
found to be stable.
Example 10
[0086] 62.5 g of Example 2 was dissolved in 585 mL of
CH.sub.2Cl.sub.2 followed by the addition of 12.5 g of oleic acid.
Separately, a base solution composed of 3.75 g of ethanolamine, 3 g
of Triton X-100.TM. and 2.6 g of Elvanol.TM. in 95 mL of distilled
water was prepared. The rubber cement was added to a high speed
blender, and the base solution was slowly added. Upon completion of
saponification (.about.5 minutes after addition of base solution),
125 mL of distilled water was added to the blender. The surfactant
concentration on a dry weight basis was 25.9%. The mixture was
continued to blend with an air purge over the top of the blender
opening. After 1.5 h of mixing, the latex was separated and the
solids content was determined to be 14%. The ionomer latex was
found to be stable.
Example 11
[0087] 62.5 g of Example 2 was dissolved in 585 mL of
CH.sub.2Cl.sub.2 followed by the addition of 12.5 g of oleic acid.
Separately, a base solution composed of 3.75 g of ethanolamine, 3 g
of Triton X-100.TM. and 2.6 g of Elvanol.TM. in 95 mL of distilled
water was prepared. The rubber cement was added to a high speed
blender, and the base solution was slowly added. Upon completion of
saponification (.about.5 minutes after addition of base solution),
65 mL of distilled water was added to the blender. The mixture was
continued to blend with an air purge over the top of the blender
opening. After 1.5 h of mixing, the latex was separated and the
solids content was determined to be 26%. The ionomer latex was
found to be stable.
Example 12
[0088] 10 phr (based on 11 wt % solids) was added to Example 9. The
solution was mixed for 2.5 hours and results in a stable latex
whereby no separation of the latex was observed.
Example 13
[0089] 10 phr of Microlite 923 (based on 11 wt %) was added to
Example 9. The solution was mixed for 2.5 hours and resulted in a
well dispersed, stable latex whereby no separation was
observed.
Example 14
[0090] 10 phr of Cloisite 15A (based on 11 wt %) was added to
Example 9. The solution was mixed for 2.5 hours and resulted in a
stable latex whereby no separation of the latex was observed.
Example 16
[0091] 10 phr Mistron HAR (based on 11 wt %) was added to Example
9. The solution was mixed for 2.5 hours and resulted in a stable
latex whereby no separation of the latex was observed
Example 17
[0092] 10 phr of Nanomer 1.44P (supplied by Nanocore) and 0.4 eq of
TPP (based on allylic bromide) was added to BB2030.TM. under heat
and shear conditions resulting in a butyl ionomer nanocomposite.
62.5 g of this nanocomposite was dissolved in 585 mL of
CH.sub.2Cl.sub.2 followed by the addition of 12.5 g of oleic acid.
Separately, a base solution composed of 5 g of ethanolamine, 3.69 g
of Triton X-100 and 3.4 g of Elvanol in 125 mL of hot distilled
water was prepared. The rubber cement was added to a high speed
blender, and the base solution was slowly added. Upon completion of
saponification (.about.5 minutes after addition of base solution),
700 mL of distilled water was added to the blender. The mixture was
continued to blend with an air purge over the top of the blender
opening. After 1.8 h of mixing, the latex was separated and the
solids content was determined to be 10%. The ionomer latex was
found to be stable.
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